Feb. 8, 1966 R. C.

WALKER ETAL
PURIFICATION OF BROMINE
Filed April 18, 1963

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United States Patent Office
3,233,972
PJRFICATION OF BROMENE
Robert C. Walker
assignors to TheandDow
Dougas E. Lake,
Chemical Midland,
Company, Mich,
Midland,
Mich, a corporation of Delaware
Filed Apr. 18, 1963, Ser. No. 274,014
4 Claims. (CI. 23-218)
The invention relates to a method of removing in
purities from bromine.
Pure bromine is a liquid, at standard pressure, between
the temperatures of -7.2 and 58.8 C. Below -7.2,
it is a solid and above 58.8, it is a gas. Bromine is
widely used, both as a liquid and as a gas. Among such
uses are in the preparation of disinfectants and photo
graphic materials, as an oxidizing agent generally, as an
intermediate in the manufacture of dyestuffs, drugs,
resins, and refrigerants, and in the preparation of a large
number of chemical reagents. It is widely used in the
manufacture of antiknock compounds for use in high
compression gasoline engines. It is also used in the
preparation of pharmaceuticals.
For a number of uses, bromine must be in a high state
of purity. Certain compounds are very persistent con
taminants in bromine, among which are chloroform,
ethylbromide, ethylenechlorobromide, dibromochloro
methane, carbon tetrabromide, and bromodichlorometh
ane. Chloroform is considered to be the most trouble
some of these contaminants because its boiling point is
very close to that of bromine and, accordingly, it cannot
be separated from bromine by fractional distillation.
Efforts have been made to provide better ways of sep
arating bromine from its contaminants. Among such
efforts are attempts to treat the contaminated bromine
with ultraviolet light, with mixtures of chromic acid and
sulfuric acid, and by steam distillation. One method
consists of admixing sulfuric acid with the bromine to be
purified, passing oxygen gas therethrough to produce an
effluent mixture of bromine gas and oxygen gas, Subject
ing the resulting gaseous mixture to a temperature of at
least 1000 C. to decompose the contaminants, and there
after freezing the bromine to permit its separation from
the decomposed contaminants which have a higher solidi
fication temperature.
Ultraviolet light treatment has not proved satisfactory
because a substantial portion of the impurities are not
removed thereby. Although the use of steam is satisfac
tory for the removal of some of the less volatile inpuri
ties, it leaves 25 to 50 parts per million (p.p.m.) of
known volatile impurities and 80 to 140 p.p.m. of chloro
form, which is usually present. Mixtures of sulfuric acid
and chromic acid are not fully satisfactory because of the
high decomposition rate of chromic acid in this mixture
which makes it unsuitable commercially. The practice
of the process requiring a temperature of at least 1000
C., when treating a mixture as a reactive as that of sul
furic acid and bromine, is obviously impractical for gen
eral use, Only quartz glass has shown itself to be suffi
ciently resistant to the attack of this reaction mixture to
be used in vessels in this process, and this material, is not
satisfactory for general use,
There has been an increased awareness of a desideratum
for an improved method of purifying bromine in recent
years, due to the increased demands for bromine in a
state of high purity. Heretofore this desideratum has
not been met for commercial production.
The invention, however, does meet this desideratum by
providing an improved method which is more efficient
3,233,972
Faterated Feb. 8, 1966
2
and more effective than those known heretofore. It is
a marked technical advancement over known methods
and offers the advantages of safety, economy of equip
ment and of operating costs, and produces bromine of im
proved purity.
How the method of the invention is carried out is set
forth in the ensuing description and is defined succinctly
in the appended claims.
The invention is a method of purifying bromine of or
10 ganic impurities, which consists essentially of heating the
bromine, requiring purification, at a temperature above
about 425 C. but less than about 625 C. to convert Cr
ganic impurities to bromine compounds and thereafter
Separating the bromine compounds as made from bro
15 mine by fractional distillation.
In carrying out the invention, the bromine is usually
first dried, then vaporized to a gas, thereafter heated to
a temperature greater than 425 C. and preferably at least
about 475 C. and less than 625 C. and preferably less
20 tham about 525 ° C. to convert the contaminating organic
materials present therein into brominated high boiling
compounds, and the thus heated bromine then frac
tionally distilled, whereby the bromine is volatilized off
leaving the high boiling brominated material.
25 When bromine, contaminated with organic impurities,
is subjected to heating at a temperature below about
425 C., the organic impurities present in the bronnine
are not sufficiently altered to provide for their subsequent
Separation by fractional distillation. When a tempera
30 ture above about 700° C. is employed, the organic im
purities are completely decomposed but structural ma
terials which are sufficiently resistant to corrosive attack
of bromine at such advanced temperatures and which
35
have strength properties necessary for industrial opera
tions are mot readily available.
The length of time necessary for heating the contami
nated bromine to brominate the organic contaminants
present, at the required temperature, is almost instan
40
taneous. About 0.1 of a second is considered sufficient
time. On the other hand, heating at the required tem
perature for a prolonged period of time does not in any
way defeat the objectives of the invention. However,
Such prolonged heating does not contribute to the in
45
proved purification of the bromine and is, accordingly,
not recommended for economic reasons.
The method of the invention may be practiced by pro
viding a steady flow of bromine to be purified or it may
be practiced by providing an intermittent flow as by puri
50
fying a given amount of bromine in a batch operation.
The method of the invention is best carried out as a
continuous process. The attached drawing schematically
shows an apparatus useful in the practice of the invention.
In carrying out the invention by continuous operation,
55
eimploying the apparatus of the drawing, crude bromine
to be purified is introduced through pipe 2 into vaporizer
4 where it is heated to the boiling point of bromine, where
by bromile feed is vaporized. The thus vaporized
bromine is carried upwardly and out through pipe 8 into
60 partial condenser 16, which is also maintained above the
boiling point of bromine. Some contaminants such as
H2SO4 and higher boiling organic contaminants present
in the feed bromine, are entrained in the outgoing bromine
Vapor, are Separated in partial condenser 50, and pass out
through pipe li. Gaseous bromine from partial con
denser 16 passes out through pipe 43 into reactor 4
Where the gaseous bromine is subjected to a temperature
about 425 C. and below 625 C. whereby organic con
tarninants in the bromine are converted to higher-boiling
 8,233,972.
3. 4?
brominated contaminants passes through pipe 15 into re brominated organic compounds, largely CBra. The thus,
boiler 16 where the temperature is lowered to and main heated contaminated bromine was then distilled and the
tained at the boiling point of bromine so that both liquid so distilled bromine again tested by infra spectrum and
and gaseous bromine are present therein. In the re found to be completely free from the brominated com
boiler, a still bottom portion of contaminants is removed pounds.
through pipe 18, which joins pipe 11. The gaseous EXAMPLE 2
bromine, which yet contains an appreciable portion of the The procedure of Example 1 was repeated except that
now brominated contanninants in the gaseous state, passes contaminated bromines was raised to 500 C. and then :
from the reboiler through pipe 20 into distillation column cooled. By infrared spectrum, at this point, it showed
22 which is maintained at the boiling point of bromine. O presence of between about 125-150 p.p.m. of brominated
The distillation column is conveniently filled with glass, organic compounds, largely CBra. After distillation of
porcelain, baryl, or ceramic beads, saddles, rings, or the the so treated contaminated bromine and recovery of the
like which assist in condensing and separating the higher condensed bromine, it was again tested and found to be
boiling brominated contaminants which gradually pass
downwardly in column 22 and are drawn off through pipe 15? completely free from the brominated organic compounds. .
24. Gaseous bromine, thus freed of higher boiling Test run. A
brominated contaminants, passes upwardly and out The procedure of Examples 1 and 2 was repeated except:
through overhead pipe 26 into condenser 28, where the that contaminated bromine was raised to only 400. C. and
bromine is condensed to a liquid. From condenser 28, . then cooled. After heating, it was found, by infrared
a minor portion of the liquid bromine is returned through 20 spectrum, to contain both fully brominated and un- . .
pipe 29 to the upper part of column 22 to serve as a brominated organic compounds. After distillation and
countercurrent downward liquid flow therein. The major recovery of the bromine so distilled, it was again examined
portion of the liquid bromine leaves the condenser through by infrared and found to contain less of the brominated
pipe 30 and enters washer 3i, where a flow of water enter compounds but to contain also small amounts of original
ing by way of pipe 32 absorbs HCl and HBr that may be 25 organic contaminants, e.g., CHCl3, which had not been
present in the liquid bromine and largely passes out fully brominated and therefore not removed by distillation.
through pipe 33. The liquid bromine, together with some Test run B.
water, passes through pipe 34 into separator 35. From
separator 35, the remaining water. containing any un The procedure of Examples and 2 was again repeated
removed HCl or HBr, is carried away through pipe 36 30 except that contaminated bromine was heated to only
(which joins pipe 33) and the HCl and HBr therein may 300 C. When then cooled and tested by infrared tech
be salvaged, as by passing it into an aqueous solution of niques, it was found to contain the original contaminat
caustic (not shown), e.g., an aqueous sodium hydroxide ing materials unaffected. When subsequently distilled
solution. The purified liquid bromine from separator 34 35 and again examined by infrared, the contaminated bro
passes through line 37 into drier 38, which contains a mine remained unchanged. The treatment had not re
drying medium, e.g., concentrated HSO4 acid, introduced. moved any of the organic contaminants from the bromine.
through pipe 39. The H2SO4 containing added water Reference to the examples shows that the heating tem
from the bromine passes out through pipe 41 from the perature is critical; that when heated at 400 C. or less,
drier. The liquid bromine then passes to separator. 42, the contaminants in the bromine remain incompletely
where any remaining H2SO4 is removed through pipe 43, or substantially not at all reacted and cannot be subse
which joins pipe 4. The purified and dried bromine quently, removed by distillation. It also shows that when
from the separator is passed through pipe 44 to storage. the contaminated bromine is heated at a temperature
Appropriate heating and cooling means are provided substantially above 400 C., the organic contaminants
for the various units of the apparatus as required by the are converted into higher boiling compounds which are
method of the invention. Flow control means, e.g., thereafter readily separated by distillation, leaving sub
valves, are indicated by the symbol V. stantiaily pure bromine.
Although the drawing schematically represents a suit It is clear from the marked reduction of organic im
able apparatus for carrying out the invention, it is under purities in bromine, after being heated at 400 C. and
stood that other apparatus may also be used. For ex the thus treated bromine distilled at the boiling point of
ample, a more simple apparatus may be used consisting 50 bromine, that any temperature substantially above 400 C.
essentially of only a vaporizer, reactor, and distillation (e.g., about 425 C.) but below about 625 C., at which
column; together with suitable feed lines, transfer lines, undesirable corrosivity of commonly available materials
outlet lines, and heat and flow control means. becomes pronounced, is satisfactory for the heating tem
Heat for vaporization, for reaction to brominate the perature of the invention. * ?
impurities, and for distillation may be provided by known 55 Having described our invention, what is claimed and
means and techniques employing gas or electrical means. desired to be protected by Letters Patent is:
Cooling fluids circulating through coils of conventional 1. The method of purifying bromine which is con
design may be used where reduction in temperature is taminated by low boiling organic compounds which con
desired. sists; essentially of vaporizing the contaminated bromine
In the practice of the invention by continuous opera 60 : and thereafter heating the vapors so made: at a tempera
tion, the rate of input and output is automatically con ture of at least about 425 C. and below about 625 C.
trolled, as by thermostatic controlled valves, to maintain for at least about 0.1 second to convert said low boiling
contaminants into high boiling compounds, cooling the
sufficient time for the contents of the different units of the
So heated contaminated bromine vapors to a temperature :
system, e.g., the vaporizer, reactor, and distillation column,
to be raised or lowered to the desired temperature. 65, below the boiling point of the high boiling compounds,
Examples 1 and 2 below illustrate the practice of the Subjecting the thus, successively heated, and cooled con
invention. Test runs 3 and -4 are not in accordance with taminated bromine to the boiling temperature of bromine,
the invention and are for comparative purposes. and distilling off the bromine leaving the contaminants.
EXAMPLE 1. 2. The continuous method of separating bromine from
70 low boiling organic contaminants present therein which
Bromine, having present therein contaminants com consists essentially of continuously vaporizing bromine,
prising about 100 p.p.m. chloroform, was vaporized and continuously subjecting the vaporized bromine contain-...
the resulting vapors raised in temperature to 600° C. in a ing Said low boiling organic contaminants to a reaction
vessel and then cooled. It was analyzed by infrared temperature of at least about 4.25° C. and less than about
spectrum and shown to contain about 135 p.p.m. of 75 625 C. to convert said low-boiling organic contaminants.
 3,233,972
5 6
into high boiling bromine compounds, continuously References Cited by the Examiner
fractionally distilling the thus treated bromine, at the UNITED STATES PATENTS
boiling point of bromine, whereby purified bromine gas 132,296 10/1872 Lerner et al. ——————— 23 - 218 X
is distilled over, leaving the high boiling bromine com Carter -------------- 23-218
pounds, continuously condensing the bromine gas being ? 1956993 12/1919
1324,761
5/1934 Martin ------------- 23-218
distilled over, and removing the high boiling bromine 2,016,804 10/1935 Nichols ---------- 260-652 ?
compounds remaining behind from the fractional distilla 2,784,063 3/1957 Blocket al. ---------- 23-218
tion. 2,916,506 12/1959 Axetell et al. ------- 202-61 ?
3. The method according to claim 2 wherein said reac Foulletier et al. ———— 23-21, 8 X
tion temperature is between about 475 C. and about 10 3,127.243 4/1963
3,084,028
3/1964 Konikoff ---------- 202-66 X
525 C.
4. The method according to claim 1 wherein said NORMANYUDKOFF, Primary Examiner.
heating is carried out at between about 475 C. and
about 525 C. GEORGE D. MITCHELL, Examiner.